Herbicidal N-substituted-dithioamino and N-substituted-oxythioamino triazines

ABSTRACT

Herbicidal triazine compounds of the formula   wherein X is halogen, alkylthio or alkoxy, R is hydrogen or alkyl, R1 is alkyl, R2 is alkyl, R3 is aliphatic or carbocyclic aryl and Y is sulfur or oxygen, are produced by the reaction of an N-chlorothioamino triazine and a mercapto or hydroxy compound.

United States Patent [1 1 [111 3,909,237

Cleveland Sept. 30, 1975 HERBICIDAL 3,141,885 7/1964 Ross ..260/249.8

N-SUBSTlTUTED-DITHIOAMINO AND N-SUBSTlTUTED-OXYTHIOAMINO TRIAZINES Inventor: James D. Cleveland, Albany, Calif.

Assignee: -Chevr0n Research Company, San

Francisco, Calif.

Filed: Oct. 29, 1974 Appl. No.: 518,315

Related US. Application Data Division of Ser. No. 430,321, Jan. 2, 1974, Pat. No. 3,864,342, which is a continuation-in-part of Ser. No. 251,088, May 8, I972, Pat. No. 3,796,712.

Primary E.\'aminer.lames 0. Thomas, Jr. Attorney, Agent, or Firm-J. A. Buchanan, Jr.; Dix A. Newell; Raymond Owyang [57] ABSTRACT Herbicidal triazine compounds of the formula wherein X is halogen, alkylthio or alkoxy, R is hydrogen or alkyl, R is alkyl, R is alkyl, R is aliphatic or carbocyclic aryl and Y is sulfur or oxygen, are produced by the reaction of an N-chlorothioamin0 triazine and a mercapto or hydroxy compound.

22 Claims, N0 Drawings HERBICIDAL N-SUBSTITUTED-DITHIOAMINO AND N-SUBSTITUTED-OXYTHIOAMINO TRIAZINES RELATED APPLICATIONS This application is a division of application Ser. No. 430,321, filed Jan. 2, 1974, now US. Pat. No. 3,864,342, which in turn is a continuation-in-part of application Ser. No. 251,088, filed May 8, 1972, now US. Pat. No. 3,796,712, the disclosure of which is incorporated herein by reference.

FIELD OF THE INVENTION This invention relates to triazine compounds and their use as herbicides.

Herbicidal N-trichloromethylthioamino triazines are disclosed in US. Pat. No. 3,138,445 issued June 23, 1964, to H. I-Iuemer. Herbicidal N-alkylthioamino triazines are disclosed in U.S. Pat. No. 3,141,885, issued July 21, 1964, to F. Ross. US. Pat. No. 2,907,763, issued Oct. 6, 1959, to J. F. I-Iosler, discloses 4,6- diamino-2-trichloromethyldithio triazine and its use as an herbicide.

DESCRIPTION OF THE INVENTION Compounds of the present invention may be represented by the formula (I):

wherein X is halogen of atomic number 9 to 35 (fluorine, chlorine or bromine), alkylthio of l to 4 carbon atoms or alkoxy of l to 4 carbon atoms; R is hydrogen or alkyl of l to 4 carbon atoms; R and R individually are alkyl of 1 to 4 carbon atoms, R is alkyl of l to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms, preferably 5 to 6 carbon atoms, or carbocyclic mononuclear or binuclear aryl of 6 to 12 carbon atoms substituted with up to 2 (0 to 2) fluorine, chlorine, bromine, nitro, trifluoromethyl or alkoxy of 1 to 4 carbon atoms; and Y is sulfur or oxygen.

Representative alkylthio groups which X may represent include methylthio, ethylthio, isopropylthio, npropylthio, and n-butylthio.

Representative alkoxy groups which X may represent include methoxy, ethoxy, propoxy, isopropoxy and nbutoxy.

Representative alkyl groups which R, R and R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl.

Representative alkyl R groups are methyl, ethyl, isopropyl, n-butyl, isopentyl and hexyl. Representative alkenyl R groups are vinyl, allyl, 4-pentenyl and 3- hexenyl. Representative cycloalkyl R groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Representative aryl R groups include hydrocarbyl aryl groups such as phenyl, naphthyl, phenylalkyl of 7 to 10 carbon atoms such as benzyl and 3-phenylpropyl, and phenylalkyl of 7 to 10 carbon atoms such as tolyl, xylyl, 3,4,5-trimethylphenyl, and 2,4-diethylphenyl, Representative substituted-aryl R groups include phenyl, phenylalkyl and alkylphenyl substituted with 1 to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro or alkoxy of l to 4 carbon atoms, such as 2-fluorophenyl, 3,4- dichlorophenyl, 4-bromophenyl, 2-methyl-4- chlorophenyl, 2-trifluoromethylphenyl, 4-nitropheny1, and 3-methoxyphenyl.

Preferably X is chlorine, methylthio, or methoxy; R is hydrogen; R is ethyl or isopropyl; and R is ethyl or isopropyl. More preferably R and R are the same. Preferably R is alkyl or phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of l to 4 carbon atoms. More preferably R is lower alkyl or phenyl substituted with up to 2 fluorine or chlorine.

Representative compounds of the present invention include:

2-(N-methoxythio-N-methylamino)-4-methylamino- 6-chloro-l ,3,5-triazine, 2-(N-allyloxythio-N-methylamino)-4-ethylamino-6- fluoro- 1 ,3 ,S-triazine, 2-(N-cyclohexoxythio-N-ethylamino)-4-ethylamino- 6-chlorol ,3 ,S-triazine, 2-(N-phenoxythio-N-butylamino)-4-propylamino-6- bromo-1,3 ,S-triazine, 2-(N-a-methylnaphthoxythio-N-ethylamino)-4- isopropy1amino-6-chloro- 1 ,3,5-triazine, 2-(N-benzyloxythio-N-isopropylamino)-4- ethylamino-6-ch1orol ,3 ,S-triazine, 2-(N-4-nitrobenzyloxythio-N-isopropy1amino)-4- isopropylamino-6-chloro-l ,3,5-triazine, 2-(N-4-chlorophenoxythio-N-isopropy1amino)-4- ethylamino-6-methylthio-l ,3,5-triazine, 2-(N-3-tolylthio-N-ethy1amino)-4-isopropylamino-6- methylthio- 1 ,3 ,S-triazine, 2-(N-ethyldithio-N-t-butylamino)-4-ethylamino-6- methylthio- 1 ,3 ,5-triazine, 2-(N-allyldithio-N-methylamino)-4-methylamino-6- methylthiol ,3 ,S-triazine, 2-(N-cyclohexyldithio-N-ethylamino)-4-ethylamino- -ethylthiol ,3 ,S-triazine, 2-(N-phenyldithio-N-methylamino)-4-propylamino- 6-isopropylthio-1 ,3 ,5-triazine, 2-(N-naphthyldithio-N-isopropylamino )-4- ethyIamino-6-n-butylthio- 1,3,5-triazine, 2-( N-2,4-dimethylphenyldithio-N-isopropylamino) 4-ethylamino-6-methoxy-1 ,3 ,S-triazine, 2-(N-4-chlorobenzyldithio-N-ethylamino)-4- isopropylamino-6-methoxy-l ,3 ,5-triazine, 2-(N-2-f1uorophenyldithio-N-isopropylamino )-4- isopropylamino-6-methoxyl ,3 ,5-triazine, 2-(N-4-methoxyphenyldithio N-t-butylamino )-4- methylamino-6-ethoxy-1 ,3 ,S-triazine, 2-(N-4-methoxyphenyldithio-N-methylamino )-4- methy1amino-6-isopropoxy-1 ,3 ,S-triazine, 2-( N-3-bromophenyldithio-N-methylamino)-4- dimethylamino-6-chlorol ,3 ,5-triazine,

2-(N-2-trifluoromethylphenyldithio-N- methylamino)-4-diethylamino-6-methylthio-1 ,3 ,5 triazine, and

2-( N-3-bromo-4-chlorophenyldiothio-N- methylamino)-4-methylethylamino-6-methoxy- 1 ,3,5-triazine.

The triazine compounds of the invention are prepared in accordance with the following reaction (1):

wherein R, R, R R" and Y are as defined above, and

B is an acid acceptor.

as Z-methylpyridine, Z-ethylpyridine, methylpyridine, 3,5-dimethylpyridine, and 2- butylpyridine. Suitable trialkylamines are those wherein the alkyl group contains individually l to 4 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine. The preferred acid acceptors are pyridine compounds, especially pyridine.

The N-chlorothio urea reactant (ll) and the mercapto or hydroxy compound ([1]) are employed in substantially equimolar amounts, e.g., the molar ratio of the N-chlorothio urea reactant (II) to the mercapto or hydroxycompound (Ill) generally varies from about l.5:l to l:l.5, although molar ratios of (ll) to (III) of about 1.2:1 to l:l.2 are preferred. The molar ratios of acid acceptor to the N-chlorothio urea reactant are also substantially equimolar, e.g., the molar ratio of acid acceptor to N-chlorothio urea reactant varies from about l .5 :l to l:l.5, although molar ratios of acid acceptor to Nchlorothio urea reactant of about 1.221 to l:l.2 are preferred.

The reaction is generally accomplished by reacting the N-chlorothio urea reactant (ll) and the mercapto or hydroxy compound (III) in the presence of the acid acceptor in the liquid phase in an inert diluent. Suitable inert diluents for the reaction include alkanes of 5 to carbon atoms, such as hexane, isooctane and decane; aromatic compounds such as benzene and chlorobenzene; oxygenated hydrocarbons such as acyclic alkyl ethers, e.g., dimethoxyethane and dibutyl ether; and cycloalkyl ethers, e.g., dioxane, tetrahydrofuran and tetrahydropyran. Other suitable diluents include nitriles such as acetonitrile and propionitrile; dialkylamides such as dimethylformamide and dialkylsulfoxides such as dimethylsulfoxide. Preferred diluents are chlorinated hydrocarbons of l to 2 carbon atoms, such as methylene dichloride, chloroform, carbon tetrachloride and ethylene dichloride. Generally, the amount of diluent employed ranges from 1 to 50 mols per mol of N-chlorothio urea reactant.

The reaction is suitably conducted at a temperature between C. and the boiling point of the diluent, although temperatures between O and 50C. are preferred. The reaction is conducted at or above atmospheric pressure.

The triazine product (I) is recovered and purified by conventional procedures such as extraction, crystallization, chromatography, etc.

The N-chlorothioamino triazine reactant (ll) is prepared in accordance with the following reaction (2):

wherein R, R, R and X have the same significance as previously defined and B is an acid acceptor.

When the triazine reactant (ll) has R as hydrogen and R and R as different groups, a mixture of N- chlorothioamino triazines is generally obtained.

The acid acceptor is an organic base having no N-l-l groups, such as a pyridine compound or a trialkylamine compound. Suitable pyridine compounds are pyridine and pyridine compounds of 6 to 10 carbon atoms and of l to 2 alkyl groups such as 2-methylpyridine, 2- ethylpyridine, 3-methylpyridine, 3,5-dimethylpyridine, and 2-butylpyridine. Suitable trialkylamines are those wherein the alkyl group contains individually l to 4 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine.

The sulfur dichloride and the triazine compound (IV) are employed in substantially equimolar amounts, e.g., the molar ratio of sulfur dichloride to the triazine compound generally varies from about 1.5:1 to 1:1.5, although molar ratios of sulfur dichloride to the triazine compound of 1.4:1 to 1.1:l are preferred. The molar ratio of acid acceptor to sulfur dichloride is also substantially equimolar, e.g., the molar ratio of acid acceptor to sulfur dichloride varies from about 1.2:1 to 1:12, although molar ratios of acid acceptor to sulfur dichloride of 1:1 to 1:12 are preferred.

In order to produce the N-chlorothioamino triazine reactant (II) in high yield, it is essential to react the triazine compound (IV) and sulfur dichloride in the presence of a limited amount of free, uncomplexed (unreacted) acid acceptor. This is suitably accomplished by the addition of the acid acceptor to a substantially equimolar mixture of the triazine reactant and the sulfur dichloride so that the mols of free acid acceptor to the total mols of triazine reactant and N-chlorothio triazine product is less than 0.2:1, preferably less than O.l:l and more preferably less than 0.05:1. In other words, during the course of the reaction between the sulfur dichloride and the triazine reactants, there should be at least 5 mols of the triazine reactant and the is not complexed with hydrochloric acid. Provided that the reaction is conducted with the restricted amount of acid acceptor indicated above, the contacting of the acid acceptor with the mixture of the triazine and the sulfur dichloride can be conducted by a variety of procedures. In one modification, the acid acceptor is added in increments, e.g., dropwise, in an inert diluent, if desired, to a mixture of the triazine and sulfur dichloride in an inert diluent. in another modification, the acid acceptor is added continuously to a mixture of the triazine and sulfur dichloride in an inert diluent.

Suitable inert diluents for the reaction (2) include alkanes of 5 to 10 carbon atoms, such as hexane, isooctane and decane; aromatic compounds such as benzene and chlorobenzene; oxygenated hydrocarbons such as acyclic alkyl ethers, e..g., dimethoxyethane and dibutyl ether; and cycloalkyl ethers, e.g., dioxane, tetrahydrofuran and tetrahydropyran. Other suitable diluents include nitriles such as acetonitrile and propionitrile; dialkylamides such as dimethylformamide, and dialkylsulfoxides such as dimethylsulfoxide. Preferred diluents are chlorinated hydrocarbons of 1 to 2 carbon atoms, such as methylene dichloride, chloroform, carbon tetrachloride and ethylene dichloride. Generally, the amount of diluent employed rangesfrom 1 to 50 mols per mol of sulfur dichloride.

The reaction (2) is suitably conducted at a temperature between C. and the boiling point of the diluent, although temperatures between 0C. and 50C. are preferred. The reaction is conducted at or above atmospheric pressure.

The N-chlorothio urea (11) is suitably isolated from the reaction mixture by conventional procedures such as extraction, distillation, chromatography, etc. Alternatively, a solution of the N-chlorothio urea in the reaction diluent, preferably after removal of the acid acceptor hydrochloride salt produced in the reaction, is reacted with the mercapto or hydroxy compound (111) according to reaction l to produce the triazine product (l) of the invention.

The preparation of the triazines of the invention is illustrated by the following examples.

EXAMPLE 1 Preparation of 2-(N-chlorothio-N-ethylamino)-4-ethylamino-6- chloro-l ,3 ,5-triazine 2,4-Bis-(ethylamino)-6-chloro-S-triazine 10.08 g (0.05 mol) was slurried in methylene chloride. Sulfur dichloride, 5.67 g (0.055 mol) was then added to the slurry at room temperature. Pyridine (4.74 g, 0.06 mol) was then added dropwise over a period of 10 minutes to the slurry at a temperature between 30C. The reaction mixture was stirred for minutes at room temperature and filtered to remove the pyridine hydrochloric product. The filtrate solution which contained the 2-(N-chlorothio-N-ethylamino)-4-ethylamino-6- chloro-l ,3,5-triazine product was analyzed by nuclear magnetic spectroscopy. The methylene hydrogens of the N-chlorothio-N-ethylamino group appeared as a quartet at 3.95 8 (relative to tetramethylsilane).

EXAMPLE 2 Preparation of 2-( N-phenyldithio-N-ethylamino)-4-ethylamino-6 chloro- 1 ,3 ,5-triazine A solution of about 0.05 mol of 2-(N-chlorothio-N- ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine in methylene dichloride was prepared as described in Example 1. Benzenethiol (4.95 g, 0.045 mol) and pyridine (3.95 g, 0.05 mol) dissolved in 10 ml of methylene dichloride were then added dropwise to the solution of the N-chlorothioamino triazine at 0C. over a period of 5 minutes. Ten minutes after the addition was complete, the reaction was washed with water, washed with sodium bicarbonate solution, dried over magnesium sulfate, and evaporated under reduced pressure to yield a brown semi-solid. Chromatography over silica gel (chloroform eluent) gave the triazine product as an offwhite solid, m.p., 1 l0-l 11C. Elemental analysis showed: %S, calc. 18.7, found 18.1; %Cl, calc. 10.4, found 11.1.

EXAMPLE 3 Preparation of 2-( N-methyldithio-N-ethylamino)-4-ethylamino-6- chloro- 1 ,3 ,S-triazine 2,4-Bis-(ethylamino)-6-chloro-S-triazine (10.08 g, 0.05 mol) was slurried in methylene chloride. Sulfur dichloride (5.67 g, 0.055 mol) was then added to the slurry at room temperature. Pyridine (4.74 g, 0.06 mol) was then added dropwise over a period of 10 minutes at a temperature of between 2530C. The reaction mixture was stirred for 30 minutes at room temperature and filtered to remove the pyridine hydrochloride.

Methyl mercaptan (2.16 g, 0.045 mol) and pyridine (3.95 g, 0.05 mol) dissolved in 10 ml of methylene chloride was then added dropwise to the filtrate solution of the N-chlorothioamino triazine at 0C. over a period of 5 minutes. Ten minutes after the addition was complete, the reaction was washed with water, washed with sodium bicarbonate solution, dried over magnesium sulfate, and evaporated under reduced pressure to yield a brown semi-solid. Chromatography over silica gel (benzene eluent) yielded the triazine product as a white solid, m.p., 100102 C. Elemental analysis showed: %S, calc. 22.9, found 22.9; %Cl, calc. 12.7, found 13.0.

EXAMPLE 4 Preparation of 2-(N-methoxythio-N-ethylamino)-4-ethylamino-6- chloro-1,3 ,S-triazine A solution of about 0.05 mol of 2-(N-chlorothio-N- ethylamino)-4-ethylamino-6-chloro-1,3 ,S-triazine in methylene dichloride was prepared as described in Example 1. Methanol (1.6 g, 0.05 mol) and pyridine (3.95

g, 0.03 mol) dissolved in 10 ml of methylene chloride was added dropwise to the solution of the N- chlorothioamino triazine over, a period of 5 minutes. Ten minutes after the addition was complete, the reaction mixture was washed with water, washed with sodium bicarbonate solution, dried over magnesium sulfate, and evaporated under reduced pressure to yield a brown oil. Chromatography. over silica gel (benzene and 5% ethyl ether/% benzene eluents) yielded the 2-(N-methoxythio-ethylamino)-4-ethylamino-6- chloro-l,3,5-triazine product, as a white solid, m.p. 9597.5. Elemental analysisshowed: %S, calc. 12.2, found 12.2, %Cl, calc. 13.5, found 13.3.

EXAMPLE 5 Herbicidal Tests The triazine compounds of the invention are, in general, herbicidal in both preand post-emergent applications. For pre-emergent control of undesirable vegetation, these triazines will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergent applications, the triazine compounds will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

The triazine compounds of the present invention can be used alone as herbicides. However, it is generally desirable to apply the compounds in herbicidal compositions comprising one or more of the herbicidal compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent or a solid, e.g., in the form of dust powder or granules. In the herbicidal composition, the active herbicidal compounds can be from about 0.01 to 95% by weight of the entire A composition.

Suitable liquid diluent carriers include water and organic solvents, e.g., hydrocarbons such as benzene, toluene, kerosene, diesel oil, fuel oil, and petroleum naphtha. Suitable solid carriers are natural clays such as kaolinite, atalpulgite, and montmorillonite. In addition, talcs, pyrophillite, diatomaceous silica, synthetic fine silicas, calcium aluminosilicate and tricalcium phosphate are suitable carriers. Organic materials such as walnut-shell flour, cottonseed hulls, wheat flour, wood flour or redwood-bark flour may also be used as solid carriers.

7 8 used; representing no phytotoxicity, 100 representing complete kill. j

v Post-Emergent Test The test triazine was formulated in the same manner as described above for the pre-emergent test. The concentration of the triazine in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 similar pots of 24-day-old plants (approximately to 25 plants per pot) at a dose of 100 micrograms per cm After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the triazine was rated based on these observations. A O-to-lOO scale was used; 0 representing no phytotoxicity, lOO representing complete kill.

The herbicidal composition will also usually contain The results of these tests appear in Table I.

TABLE 1 Herbicidal Efi'ectiveness Pre/Post Compound O W C M P L 2(N-phenyldithio-N-ethylamino)-4- ethylamino--chlorol ,3 ,S-triazine lOO/ l 00 70/ l 00 100/80 100] l 00 lOO/ 1 O0 lOO/ 1 0O 2-(N-methyldithio-N-methylamino)-4- I ethylamino-6-chl0rol ,3 ,S-triazine lOO/ l 00 l 00/ l 00 1 00/100 100/100 I00] 1 0O lOO/ l 00 2-( N-methoxythio-N-ethylamino )-4- ethylamino-6-chloro-l ,3,S-triazine 100/100 100/100 100/50 1 00/100 lOO/ I 00 100/100 0 Wild Oats (Avenua Fatua) C Crabgrass (Digilaria sanguinalis) P Pigweed (Amaramlms relroflexus) aiminor amount of a surface-active agent. Such surface agents are those commonly known as wetting agents, dispersing agents and emulsifying agents, and can be anionic, cationic or nonionic in character. The herbicidal compositions may also contain other pesticides, adjuvants, stabilizers, conditioners, fillers and the like.

The amount of herbicidal compound or composition administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application i.e., sheltered areas such as greenhouses, as compared to exposed areas such as fields as well as the desired type of control. Generally, for both preand postemergent control, the herbicidal compounds of the invention are applied at rates of 2 to 60 kg/ha, and the preferred rate is in the range of 5 to 40 kg/ha.

Preand post-emergent herbicidal tests on the triazines prepared in Examples 2-4 were made using the following methods:

Pre-Emergent Test An acetone solution of the test triazine was prepared by mixing 750 mg. triazine, 220 mg. of a nonionic surfactant and ml. of acetone. This solution was added to approximately 125 ml. of water containing 156 mg. of surfactant. 7

Seeds of the test vegetation were planted in a pot of soil and the triazine solution was sprayed uniformly onto the soil surface at a dose of 100 micrograms per cm. The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc., for a 3 week period. At the end of this period the herbicidal effectiveness of the triazine was rated based on the physiological observations. A O-to-lOO scale was W Water grass (Echinochloa crusgalli) M Mustard (Brassica arvensis) L Lambsquarter (Chenapadium album) What is claimed is:

1. A method for the control of undesirable vegetation which comprises applying thereto a herbicidally effective amount of a triazine compound of the formula wherein X is fluorine, chlorine, bromine, alkoxy of l to 4 carbon atoms, or alkylthio of l to 4 carbon atoms, R is hydrogen or alkyl of l to 4 carbon atoms, R is alkyl of l to 4 carbon atoms, R is alkyl of l to 4 carbon atoms, R is alkyl of l to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or carbocyclic mononuclear or binuclear aryl of 6 to 12 carbon atoms and of up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro or alkoxy of l to 4 carbon atoms, and Y is oxygen or sulfur.

2. The method of claim 1 wherein X is chlorine, me-

thoxy or methylthio.

3. The method of claim 1 wherein R is hydrogen.

4. The method of claim 1 wherein R and R are ethyl or isopropyl.

5. The method of claim 1 wherein X is chlorine, R is hydrogenand R and R are ethyl.

6. The method of claim 1 wherein R is alkyl and Y is sulfur.

7. The method ofclaim 1 wherein the compound is 2-(N-rnethylditliio-N-ethylamino)-4-ethylamino-6- chlorol ,3 ,S-triazine.

8. The method of claim 1 wherein R is phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, alkyl of l to 4 carbon atoms or alkoxy of l to 4 carbon atoms.

9. The method of claim 1 wherein R is phenyl substi-' wherein X is fluorine, chlorine, bromine, alkoxy of 1 to 4 carbon atoms, or alkylthio of l to 4 carbon atoms, R is hydrogen or alkyl of 1 to 4 carbon atoms, R is alkyl of l to 4 carbon atoms, R is alkyl of l to 4 carbon atoms, R is alkyl of l to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, cycloalkyl of 3 to 8 carbon atoms or carbocyclic mononuclear or binuclear aryl of 6 to 12 carbon atoms and of up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro or alkoxy of l to 4 carbon atoms, and Y is oxygen or sulfur, and a biologically inert carrier.

13. The composition of claim 12 wherein X is chlorine, methoxy or methylthio.

14. The composition of claim 12 wherein R is hydrogen.

15. Thecomposition of claim 12 wherein R and R are ethyl or isopropyl.

16. The composition of claim 12 wherein X is chlorine, R is hydrogen and R and R are ethyl.

17. The composition of claim 12 wherein R is alkyl and Y is sulfur.

18. The composition of claim 12 wherein the compound is 2-( N-methyldithio-N-ethylamino)-4- ethylamino-6-chloro l ,3 ,S-triazine.

19. The composition of claim 12 wherein R is phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.

20. The composition of claim 12 wherein R is phenyl substituted with up to 2 fluorine or chlorine and Y is sulfur.

21. The composition of claim 12 wherein R is alkyl and Y is oxygen.

22. The composition of claim 21 wherein the compound is 2-(N-methoxythio-N-ethylamino)-4- ethylamino-6-chlorol ,3,5-triazine. 

1. A METHOD FOR THE CONTROL OF UNDESIRABLE VEGETATION WHICH COMPRISES APPLYING THERETO A HERBICIDALLY EFFECTIVE AMOUNT OF A TRIAZINE COMPOUND OF THE FORMULA
 2. The method of claim 1 wherein X is chlorine, methoxy or methylthio.
 3. The method of claim 1 wherein R is hydrogen.
 4. The method of claim 1 wherein R1 and R2 are ethyl or isopropyl.
 5. The method of claim 1 wherein X is chlorine, R is hydrogen and R1 and R2 are ethyl.
 6. The method of claim 1 wherein R3 is alkyl and Y is sulfur.
 7. The method of claim 1 wherein the compound is 2-(N-methyldithio-N-ethylamino)-4-ethylamino-6-chlorO-1,3,5-triazine.
 8. The method of claim 1 wherein R3 is phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
 9. The method of claim 1 wherein R3 is phenyl substituted with up to 2 fluorine or chlorine and Y is sulfur.
 10. The method of claim 1 wherein R3 is alkyl and Y is oxygen.
 11. The method of claim 10 wherein the compound is 2-(N-methoxythio-N-ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine.
 12. An herbicidal composition comprising an herbicidally effective amount of a triazine compound of the formula
 13. The composition of claim 12 wherein X is chlorine, methoxy or methylthio.
 14. The composition of claim 12 wherein R is hydrogen.
 15. The composition of claim 12 wherein R1 and R2 are ethyl or isopropyl.
 16. The composition of claim 12 wherein X is chlorine, R is hydrogen and R1 and R2 are ethyl.
 17. The composition of claim 12 wherein R3 is alkyl and Y is sulfur.
 18. The composition of claim 12 wherein the compound is 2-(N-methyldithio-N-ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine.
 19. The composition of claim 12 wherein R3 is phenyl substituted with up to 2 fluorine, chlorine, bromine, trifluoromethyl, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
 20. The composition of claim 12 wherein R3 is phenyl substituted with up to 2 fluorine or chlorine and Y is sulfur.
 21. The composition of claim 12 wherein R3 is alkyl and Y is oxygen.
 22. The composition of claim 21 wherein the compound is 2-(N-methoxythio-N-ethylamino)-4-ethylamino-6-chloro-1,3,5-triazine. 